Just wanted to share the results of an experiment, to see how well some impure harmala alkaloid extract can be purified by recrystallising with methanol. First attempt yielded crystals.

The method was to stir 2g of the crude alkaloids in 50 ml of boiling methanol, filter, and put in an evaporating dish on a hotplate on low heat. The methanol evaporated fast and left what you see in the pictures. Another evaporating dish was left to evaporate at room temperature but that one didn't form big crystals, just tiny powder like ones. The yield was about 400mg in total. Much of the crude alkaloids were left behind in the filter, using bigger volume of methanol would maybe dissolve them all.

These harmalas were extracting from ayahuasca (brew containing vine + chacruna).

That's not technically what recrystallisation is, but nice results all the same.

True recrystallisation relies on a solubility difference with change of temperature. If you had achieved the crystallisation by cooling the methanol solution, then it would have been a recrystallisation. The important part of the process is that the compound of interest crystallises out and impurities, being present in lesser amounts , remain in solution. This allows the product to be cleaned up considerably.

By allowing the solvent to evaporate completely here, you have caused whatever impurities there may have been in solution to remain in the dish. The purification part here was the dissolving in methanol and the subsequent filtration.

It's interesting that the rapid evaporation left larger crystals than the slower one. Did you cover the dishes to keep out dust and other foreign material?

Perhaps you could use some of the bigger crystals as seeds for another slow evaporation, although you'd have to be sure the solution was saturated enough before adding one. You've got a few nice, pale clusters to use there.

How did you extract the harmalas from a vine + chacruna brew? Are you sure none of these crystals is DMT?

I just diluted the brew with water until it was no longer viscous then added saturated KOH solution and let it sit until the precipitated alkaloids settled on the bottom of the Beaker, then cleaned the alkaloids by decanting and diluting repeatedly. Then dissolved the alkaloids in vinegar, filtered, rebasified, vacuum filtered and washed with distilled water. Let the alkaloids dried the alkaloids. I don't think there's any significant quantity of DMT in there.

The alkaloids have turned red over time:


It looks like they're oxidizing. It's interesting because the same alkaloids purified through a series of A/B extractions remain white, they don't change color over time. I don't know what the explanation behind this is.

But how do you know that? Have you done any TLC to check, or washed them with warm naphtha to preferentially dissolve DMT? It's worth knowing the composition of your extract a bit more precisely than just making an assumption. That way you could avoid some surprises, be they psychological or legal.

Maybe it's the DMT turning red 🙃

But seriously, DMT is exceedingly soluble in ethanol at least and it seems likely that it would have a reasonable solubility in methanol, greater than that of the harmala alkaloids. As the methanol evaporates, first the harmalas start crystallising and what remains in solution is an ever-increasing concentration of DMT. Eventually this forms a layer on the harmala crystals, even if there was only a small concentration of DMT in the crude alkaloid mix to start with. It could be this outer layer of DMT oxidising - although harmala extracts are known to form 'harmala red' when allowed to evaporate in ethanolic solution. So it's also fairly likely to be down to the fact that you evaporated an alcoholic solution - methanol in your case, of course.

Try having a play with the red stuff to see if you can separate it somehow. And if you succeed in washing the crystals so that they're freed from the red material, try dissolving them, or at least a sample of them, in some more methanol in order to repeat the evaporation and oxidation process. Then we can find out whether the cleaned crystals will turn red again.

I think ethyl acetate re-x's harmalas pretty well based on early observations. I'll be posting results eventually, but maybe worth considering for those wanting to experiment.

On that note, butyl acetate appears to show promise with harmalas as well. Things are in the pipeline on this side too. Just to add another option to the table.